CN103666482A - Novel smectic phase A liquid crystal material - Google Patents

Novel smectic phase A liquid crystal material Download PDF

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CN103666482A
CN103666482A CN201210331994.6A CN201210331994A CN103666482A CN 103666482 A CN103666482 A CN 103666482A CN 201210331994 A CN201210331994 A CN 201210331994A CN 103666482 A CN103666482 A CN 103666482A
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liquid crystal
general formula
smectic
atom
formula
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CN103666482B (en
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李文磊
孙刚
尹环
谭志先
翟怀彬
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Chongqing Hanlang Precision Technology Co ltd
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HALATION PHOTONICS CO Ltd
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Priority to PCT/CN2012/082167 priority patent/WO2014036766A1/en
Priority to EP12884098.0A priority patent/EP2894148B1/en
Priority to JP2015530262A priority patent/JP6093862B2/en
Priority to US14/002,965 priority patent/US20140160384A1/en
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Abstract

The invention relates to a novel smectic phase A liquid crystal material which comprises at least one heterocyclic compound shown as a formula (I), in which X and Z are benzene rings, F is a fluorine atom, any one hydrogen atom on the benzene rings can be substituted by the fluorine atom. When Y is the benzene ring, T is a nitrogen atom, and any one carbon atom on the benzene ring can be substituted by the nitrogen atom. When Y is a cyclohexyl ring, T is an oxygen atom, a sulfur atom and/or a boron atom, any one carbon atom on the cyclohexyl ring can be substituted by the oxygen atom, the sulfur atom and/or the boron atom. The smectic phase A liquid crystal material provided by the invention further comprises at least one ester compound and an ester compound shown as the a formula (II). By applying the material to a display apparatus, displayed images placed or driven to use for a long time can be completely erased without ghosts, the contrast of the display apparatus is high and is commonly greater than 10, and the driving voltage is low and is commonly 20-50V.

Description

Novel smectic A phase liquid crystal material
Technical field
The present invention relates to the novel smectic A of class phase liquid crystal material, belong to optics display material technical field.
Background technology
Liquid crystal is by different being mainly divided into mutually: nematic phase, smectic phase, cholesteryl phase, divide again smectic A, B, C, D, E, F, G, H, I, G to equate in smectic phase.The viscosity of nematic phase and cholesteric liquid crystal is low, have obvious mobility, and the viscosity of smectic liquid crystal is larger.Liquid crystal all has dielectric anisotropy, and liquid crystal molecule can be by electric field driven.After the liquid crystal molecule that viscosity is low is driven by electrical signal, because viscosity is low, after cut-out electrical signal, molecular arrangement can not keep, and can also return to original ordered state; After but the liquid crystal molecule that viscosity is high is driven by electrical signal, because viscosity is high, after cut-out electrical signal, molecular arrangement state is held, and can not return to original ordered state and can only maintain current state.So smectic liquid crystal is as showing, remove electrical signal after driven, still can keep displaying contents, there is memory effect.As shown in Fig. 1-a, Fig. 1-b and Fig. 1-c, Fig. 1-a is the state that shows image, and Fig. 1-b is the state that the image of demonstration cannot be wiped ghost, and Fig. 1-c is the state that image can be wiped completely.
D.Coates in 1978 etc. have described the photoelectricity drive characteristic of a kind of smectic A phase compound 8CB in " Electrically induced scattering textures in smectic A phases and their electrical reversal " literary composition.The smectic such as 8CB, 8OCB A phase material as the shortcoming of smectic A phase liquid-crystal display clearly at that time: driving voltage high (generally in 200V left and right), before use, need one " aging " period by stabilized driving, can only in one section of narrow temperature range (10 ° of C left and right), drive.
Dow Corning company is in the patent of GB2274649A in 1994, the type siloxane smectic A phase liquid crystal material of finding can reduce driving voltage (70 ~ 100V left and right), do not need long-time " aging " just energy steady operation, can widen to some extent in actuation temperature interval yet.Cambridge industry utilizes this class siloxanes liquid crystal material and nematic phase formula to be mixed and has obtained wide temperature smectic A phase material in WO2010/070606, and a nearlyer step has been widened the use temperature of smectic category-A material.In WO 2011/115611A1, Cambridge industry has also been mentioned and has been utilized types of silicone polymers to carry out being mixed of smectic A phase dispensing liquid crystal.Type siloxane smectic A phase material, not only itself has smectic A phase, can also induce other non-smectic A phase materials, makes to have smectic A phase with the mixed mixing material of siloxanes liquid crystal material.So type siloxane smectic A phase liquid crystal material is a class material very important during smectic A fills a prescription mutually.
Yet type siloxane smectic A phase liquid crystal, its memory effect is very strong, and the image of demonstration can not thoroughly be wiped free of, and easily leaves the ghost (as shown in Figure 1 b) of shown image.In addition the degree of birefringence due to type siloxane smectic A phase material itself very little (Δ n ≈ 0.08), and the usage quantity of siloxanes liquid crystal is larger in formula, so it is not high to take the smectic A phase dispensing liquid crystal degree of birefringence that siloxanes is main body.And contrast gradient is relevant with the degree of birefringence of liquid crystal material in diffuse transmission type display format, the larger contrast gradient of degree of birefringence is higher, so contrast gradient is poor when type siloxane smectic A phase material is used as demonstration.
Summary of the invention
The object of the present invention is to provide the smectic A phase liquid crystal material that a class is new, eliminate the demonstration ghost of siloxanes liquid crystal smectic A phase formula system, and improve contrast gradient.
The present invention studies and finds that a class can induce the material of smectic phase, and has carried out based on this liquid crystal and be mixed.Not only this type of smectic A phase dispensing liquid crystal does not have ghost, and contrast gradient is higher, and its driving voltage is lower (about 20 ~ 50V left and right) also.
A novel smectic A phase liquid crystal material, it comprises at least one heterogeneous ring compound representing with general formula (I).The compound that general formula (I) represents can be induced the material of smectic phase, is heterocyclic liquid crystal material, and its structure is as follows:
Figure BDA00002118739100021
Logical formula I
The positive integer that wherein n is 1 ~ 4, m and p can be 0 or 1 ~ 4 positive integer, M1 and M3 can be 0 or 1 ~ 2 positive integer, the positive integer that M2 is 1 ~ 2;
X, Z are phenyl ring, and F represents fluorine atom, and on its phenyl ring, any hydrogen atom can be replaced by fluorine atom.Y can also can be for hexamethylene ring for phenyl ring, and when Y is phenyl ring, T represents nitrogen (N) atom, and the either carbon atom on phenyl ring can be replaced by nitrogen-atoms; When Y is hexamethylene ring, T can represent oxygen (O), sulphur (S), boron (B) atom, and the either carbon atom on hexamethylene ring can be replaced by oxygen (O), sulphur (S), boron (B) atom.
A, B are selected from a kind of in following groups: CN, F, NCS, NCO, CF 3, CHF 2, CH 2f, OCF 3, OCHF 2, OCH 2f, NO 2, Cl, CH=CF 2and OCH=CF 2; Alkene oxygen base, the silylation of C1-C20 and the siloxanes of C1-C20 of the thiazolinyl of the alkyl of C1-C20, the alkoxyl group of C1-C20, C1-C20, C1-C20 and halides corresponding to above-mentioned group; Arbitrary-CH 2-quilt-O-,-S-,-CF 2-,-CF 2o-,-CO-,-COO-,-O-CO-,-O-COO-,-CF=CF-,-CH=CF-,-CF=CH-or-alkyl of C1-C20 that CH=CH-replaces is, alkene oxygen base and the isomer thereof of the thiazolinyl of the alkoxyl group of C1-C20, C1-C20 and C1-C20.
Described novel smectic A phase liquid crystal material, also comprises the ester compound that at least one represents with general formula (II).In smectic A phase liquid crystal material formula of the present invention, except above heterocycle liquid crystalline cpd, also contain esters liquid crystal compound, its structure is as shown in logical formula II:
Figure BDA00002118739100022
Logical formula II
Wherein n1, n2 are 0 or 1 ~ 4 positive integer, and n3 is 0 or 1 ~ 2 positive integer, and n4 is 0 or 1 ~ 3 positive integer.
C and D are phenyl ring, S 1and S 2for N atom or F atom, work as S 1and S 2for the arbitrary C atom of N atomic time on can substituted benzene ring, work as S 1and S 2for the arbitrary H atom of F atomic time on can substituted benzene ring.
R 1, R 2be selected from a kind of of following groups: CN, F, NCS, NCO, CF 3, CHF 2, CH 2f, OCF 3, OCHF 2, OCH 2f, NO 2, Cl, CH=CF 2and OCH=CF 2; Alkene oxygen base, the silylation of C1-C20 and the siloxanes of C1-C20 of the thiazolinyl of the alkyl of C1-C20, the alkoxyl group of C1-C20, C1-C20, C1-C20 and halides corresponding to above-mentioned group; Arbitrary-CH 2-quilt-O-,-S-,-CF 2-,-CF 2o-,-CO-,-COO-,-O-CO-,-O-COO-,-CF=CF-,-CH=CF-,-CF=CH-or-alkyl of C1-C20 that CH=CH-replaces is, alkene oxygen base and the isomer thereof of the thiazolinyl of the alkoxyl group of C1-C20, C1-C20 and C1-C20.
Described novel smectic A phase liquid crystal material, also comprises at least one ionic compound.In smectic A phase dispensing liquid crystal provided by the invention, also must add ionic compound.
In novel smectic A phase liquid crystal material of the present invention, general formula (I) and (II) content of the compound of expression can be the 1wt%～100wt% of mixed liquid crystal stratum total, and preferred content is 10wt%～100wt%; Ionic compound content can be the 0.0001wt% ~ 10wt% of mixed liquid crystal stratum total, and preferred content is 0.0001wt% ~ 1wt%.
In smectic A phase dispensing liquid crystal of the present invention, except above logical formula I heterocycle liquid crystal material, outside logical formula II ester liquid crystal material, can also add nematic liquid crystal formula, to row liquid crystal monomer, other types liquid crystal monomer or do not show the bar-shaped compound of liquid crystal characteristic.
In addition, in described novel smectic A phase liquid crystal material, also can further add dichroic dye, UV glue etc.
With regard in smectic A phase dispensing liquid crystal of the present invention, logical formula I heterogeneous ring compound, leads to the further classification of formula II ester compound and ionic compound and preferable case and is described in detail below.
1, heterogeneous ring compound:
(1) the heterocyclic liquid crystalline cpd shown in the logical formula I using in the present invention, when Y is phenyl ring, T while being nitrogen-atoms, the pyridine compounds and their that preferred formula (III) represents.
Logical formula III
In general formula III, letter character A, B, X, Z, F, m, p, M1, M2, M3 representative implication are with logical formula I.
(2) the heterocyclic liquid crystalline cpd as shown in logical formula I using in the present invention, when Y is phenyl ring, T while being nitrogen-atoms, the miazines heterocycle liquid crystalline cpd also can preferred formula (IV) representing.
Figure BDA00002118739100041
Logical formula IV
In general formula IV, letter character representative implication is with logical formula I.
(3) the heterocyclic liquid crystalline cpd as shown in logical formula I using in the present invention, when Y is hexamethylene ring, T while being Sauerstoffatom, the dioxane class heterocycle liquid crystalline cpd that preferred formula (V) represents.
Figure BDA00002118739100042
General formula (V)
In general formula V, letter character representative implication is with logical formula I.
(4) the heterocyclic liquid crystalline cpd as shown in logical formula I using in the present invention, when Y is hexamethylene ring, T while being sulphur atom, the two sulphur six lopps heterocycle liquid crystalline cpds that preferred formula (VI) represents.
Figure BDA00002118739100043
Logical formula VI
In general formula VI, letter character representative implication is with logical formula I.
(5) the heterocyclic liquid crystalline cpd as shown in logical formula I using in the present invention, when Y partly be boracic heterocycle, preferred formula (VII) expression on dioxane, add boron class heterocycle liquid crystalline cpd.
Figure BDA00002118739100044
General formula (VII)
In general formula VII, letter character representative implication is with logical formula I.
2, ester compound:
(1) esters liquid crystal compound as shown in logical formula II using in the present invention, preferred structure is the compound that a phenyl ring is fixed on ester bond side, its structure is as shown in general formula (VIII).
General formula (VIII)
In general formula (VIII), F represents fluorine atom, and n5 is 0 or 1 ~ 4 positive integer, and the hydrogen atom on the phenyl ring on expression ester bond side can be replaced by fluorine, also can not replace, and n6 is 0 or 1 ~ 2 positive integer; Other letter rs 1, R 2, S 1, S 2, C, D, F, n1, n2, n3 implication be with logical formula II.
(i) the esters liquid crystal compound as shown in general formula (VIII) using in the present invention, C and D are phenyl ring, S 1for N atom, the arbitrary C atom on can substituted benzene ring, S 2for F atom, the arbitrary H atom on can substituted benzene ring, preferred structure is as shown in general formula (IX).
Figure BDA00002118739100052
General formula (IX)
The same general formula of alphabetical implication (VIII) in general formula (IX).
(ii) the esters liquid crystal compound as shown in general formula (VIII) using in the present invention, C and D are phenyl ring, S 1and S 2for F atom, the arbitrary H atom on can substituted benzene ring, preferred structure is as shown in general formula (X).
Figure BDA00002118739100053
General formula (X)
The same general formula of alphabetical implication (VIII) in general formula (X).
(iii) the esters liquid crystal compound as shown in general formula (VIII) using in the present invention, C and D are phenyl ring, S 1and S 2for N atom, the arbitrary C atom on can substituted benzene ring, preferred structure is as shown in general formula (XI).
Figure BDA00002118739100061
General formula (XI)
The same general formula of alphabetical implication (VIII) in general formula (XI).
(iv) the esters liquid crystal compound as shown in general formula (VIII) using in the present invention, C and D are phenyl ring, S 1for F atom, the arbitrary H atom on can substituted benzene ring, S 2for N atom, the arbitrary C atom on can substituted benzene ring, preferred structure is as shown in general formula (XII).
General formula (XII)
The same general formula of alphabetical implication (VIII) in general formula (XII).
(2) esters liquid crystal compound as shown in logical formula II using in the present invention, preferred structure is the compound that a pyridine ring is fixed on ester bond side, its structure is as shown in general formula (X III) or general formula (X IV).
Figure BDA00002118739100063
General formula (X III)
Figure BDA00002118739100064
General formula (X IV)
The same general formula of alphabetical implication (VIII) in general formula (X III) or general formula (X IV).
(i) the esters liquid crystal compound as shown in general formula (X III) or general formula (X IV) using in the present invention, C and D are phenyl ring, S 1for N atom, the arbitrary C atom on can substituted benzene ring, S 2for F atom, the arbitrary H atom on can substituted benzene ring, preferred structure is as shown in general formula (X V) or general formula (X VI).
Figure BDA00002118739100071
General formula (X V)
Figure BDA00002118739100072
General formula (X VI)
The same general formula of alphabetical implication (VIII) in general formula (X V) or general formula (X VI).
(ii) the esters liquid crystal compound as shown in general formula (X III) or general formula (X IV) using in the present invention, C and D are phenyl ring, S 1and S 2for F atom, the arbitrary H atom on can substituted benzene ring, preferred structure is as shown in general formula (X VII) or general formula (X VIII).
Figure BDA00002118739100073
General formula (X VII)
Figure BDA00002118739100074
General formula (X VIII)
The same general formula of alphabetical implication (VIII) in general formula (X VII) or general formula (X VIII).
(iii) the esters liquid crystal compound as shown in general formula (X III) or general formula (X IV) using in the present invention, C and D are phenyl ring, S 1and S 2for N atom, the arbitrary C atom on can substituted benzene ring, preferred structure is as shown in general formula (X IX) or general formula (XX).
Figure BDA00002118739100081
General formula (X IX)
Figure BDA00002118739100082
General formula (XX)
Shown in the same general formula of alphabetical implication (VIII) in general formula (X IX) or general formula (XX).
(iv) the esters liquid crystal compound as shown in general formula (X III) or general formula (X IV) using in the present invention, C and D are phenyl ring, S 1for F atom, the arbitrary H atom on can substituted benzene ring, S 2for N atom, the arbitrary C atom on can substituted benzene ring, preferred structure is as shown in general formula (XX I) or general formula (XX II).
Figure BDA00002118739100083
General formula (XX I)
Figure BDA00002118739100084
General formula (XX II)
Shown in the same general formula of alphabetical implication (VIII) in general formula (XX I) or general formula (XX II).
3, ionic compound:
In smectic A phase dispensing liquid crystal provided by the invention, ionic compound is selected from sodium lauryl sulphate, ethyltriphenylphosphiodide iodide phosphine, (ferrocenyl methyl) trimethylammonium ammonium iodide, 1,2-dimethyl-3-butyl imidazole hexafluorophosphate, tetraethyl-amine p-toluenesulfonic esters, phenyl triethyl iodate ammonium, 1-octyl group-3-Methylimidazole hexafluorophosphate, two (tetra-n-butyl amines) two (1,3-dithiole-2-thioketones-4,5-bis-mercaptan) palladium (II), tetra-n-butyl closes two (1,3-dithiole-2-thioketones-4,5-bis-mercaptan) nickel (III), two (tetra-n-butyl ammoniums) close two (1,3-dithiole-2-thioketones-4,5-bis-mercaptan) zinc, two (tetra-n-butyl ammoniums) close four cyano biphenol quinone bismethane, Tetrabutyl amonium bromide, hexadecyl ammoniumper chlorate, hexadecyl bromination four ammoniums, 1-butyl-3-Methylimidazole tetrachloro ferrate, methyl triphenyl phosphonium iodide, tetraphenylphosphoniiodide iodide phosphine, cetyl trimethylammonium bromide, cetyl trimethyl ammoniumper chlorate, cetalkonium chloride, dodecylpyridinium bromide, bromohexadecane yl pyridines, chloro-hexadecane yl pyridines, with one or more in hexadecyl tributyl phosphonium ammonium.
Novel smectic A phase liquid crystal material of the present invention can be applicable in smectic liquid crystal display device or light modulation device, is especially applied to use in the device of the double frequency drive pattern that low frequency frosted and high frequency empty.
Smectic liquid crystal drives displaying principle as shown in Figure 2.Smectic is generally to be coated with to liquid crystal display and is being mingled with mixing smectic in the middle of the upper and lower base plate of electrode layer structure and forms to liquid crystal, and mixed solution crystal layer is generally sometimes to also have mixed with polymers to form by smectic liquid crystal, conducting objects, spacer.By outside driving circuit, be connected to the capacitance structure forming on the crossed electrode of upper and lower base plate formation and apply electric flux to middle mixed solution crystal layer, the waveform applying is generally high-frequency and high-voltage driving pulse to emptying transparent operation, and low-frequency high-voltage driving pulse is to carrying out frosted operation.
(conducting objects, the organic conductive ion for example adding, as Tetrabutyl amonium bromide, sodium lauryl sulphate, cetyl trimethyl ammoniumper chlorate, tetraphenylphosphoniiodide iodide phosphine etc. for the conductive ion of (≤100Hz) long-chain shape under LCF.) can be subject to the effect of electrical forces to start back and forth movement, stir and upset the ordered arrangement of smectic layer.This behavior is similar to the dynamic scattering effect of nematic liquid crystal, different is that the eddy current plane forming in the dynamic scattering process of smectic phase is vertical with the direction of an electric field applying, and the eddy current plane forming in the dynamic scattering process of nematic liquid crystal is parallel with the direction of an electric field applying.After electrical signal stops, because smectic liquid crystal viscosity is large, thereby its molecular arrangement rests under a kind of mixed and disorderly ordered state, as shown in Fig. 2 left side, now using microscopical transmitted ray to go to observe the black state that liquid crystal cell can see that electrode district presents shading is frosted state.
Under high-frequency electric field (>=1000Hz), organic conductive ion back and forth movement becomes very little, negligible to the agitaion of liquid crystal.Now liquid crystal long axis of liquid crystal molecule under the effect of electrical forces is parallel to direction of an electric field orientation, after electrical signal stops, the arrangement of this rule is held, as shown in Fig. 2 the right, now use microscopical transmitted ray to go to observe the bright state that liquid crystal cell can see that electrode district presents printing opacity and empty state.
Certainly smectic also can rest on light through the different various states of situation to the molecular arrangement situation of liquid crystal, thereby can realize various gray level display.So smectic liquid crystal has multistable characteristic.
Lower surface analysis is the feature of a few class smectic A phase materials and the difference (as shown in Figure 3) of principle of work once.
Smectic A phase material, when emptying, is all the effect due to the dielectric anisotropy of liquid crystal itself, and liquid crystal molecule can be arranged along direction of an electric field.Frosted is the upset effect of ion that is subject to due to liquid crystal molecule, and the disturb mechanisms of dissimilar smectic A phase ion is different.So the difference of the principle of work of different smectic A phase materials is different frosted mechanism.
Fig. 3-a be take the first-generation smectic A phase material that 8CB is representative, and it has requirement to electrode surface, requires the coarse injustice of electrode surface, and needs larger initial voltage circulation to drive " aging " for some time could be by stabilized driving.Ion is wanted to play upset effect and must in smectic layer, be moved, and telemechanical direction is vertical with applied field direction, and this just requires liquid crystal material to be greater than parallel and specific conductivity (σ ‖) molecular orientation in the specific conductivity perpendicular to molecular orientation (σ ⊥).σ ‖/σ ⊥ value of 8CB is little between 0.5 to 1 its specific conductivity perpendicular to molecular orientation, and coarse electrode surface makes between adjacent uneven surface, there is the electric field perpendicular to direction of an electric field, so during low frequency driving near can first having ion to move in smectic layer in the smectic layer of coarse electrode surface, thereby drive gradually other liquid crystal layers to move together, finally reach frosted state.
Fig. 3-b be take the s-generation smectic A phase material that siloxanes liquid crystal is representative, and it can use ganoid electrode to electrode surface no requirement (NR), and do not need aging just can stabilized driving.This is that its σ ‖/σ ⊥ value is about 0.03 because this class material has the larger specific conductivity perpendicular to molecular orientation after introducing siloxane groups.Ionic additive can be enriched in the interlayer that siloxane layer is adjacent smectic layers, and while powering up, electrons, perpendicular to direction of an electric field motion between smectic layer, reaches frosted state thereby upset liquid crystal layer.
Fig. 3-c is that the smectic A of a new generation's (third generation) phase material that heterocycle liquid crystal is representative is take in the present invention, and it can use ganoid electrode to electrode surface also no requirement (NR), do not need yet aging just can stabilized driving.Because the rigid nuclear at molecule has partly been introduced heteroatoms, the specific conductivity of such material vertical direction is increased.It is inner in smectic layer that ion can be enriched in heterocycle annex, and while powering up, ion can move in direction of an electric field in smectic layer central vertical, thereby upset liquid crystal layer, reaches frosted state.During due to this class material frosted, ion is directly in smectic layer hub disturbances, frosted be easier to and smectic layer randomness higher, thereby can overcome memory effect removal of images ghost, and the scattering of light of frosted state is stronger, contrast gradient is higher.The dielectric anisotropy Δ ε of type siloxane liquid crystal is less is in addition generally 0.8 left and right, and the Δ ε of heterocyclic liquid crystal is generally greater than 8, and the larger liquid crystal of Δ ε is faster to the response of electric field, so the driving voltage of this class material is lower than type siloxane liquid crystal material.
In the novel smectic A of the present invention phase liquid crystal material formula, the function of each component is:
The component of induction smectic A phase, the heterocyclic liquid crystal shown in logical formula I plays the effect of induction smectic phase.The principle that smectic liquid crystal forms is the result that the side force gravitation of liquid crystal molecule between is greater than the end gravitation of liquid crystal molecule between, at the rigid element introducing hetero-atoms of liquid crystal molecule, can increase the lateral attraction of liquid crystal molecule between, itself be that smectic A phase time is easy to other non-smectic A phase materials to induce into smectic A phase so work as this class liquid crystal.
Increase is perpendicular to the component of molecular orientation specific conductivity (σ ⊥), and the ester liquid crystal material shown in logical formula II plays the effect that increases σ ⊥.This is because Sauerstoffatom core outer orbit is rich in lone-pair electron, joins Sauerstoffatom and heteroatoms in heterocyclic system and further acts on the specific conductivity perpendicular to molecular orientation that formation is larger, add ester liquid crystal after frosted meeting easier.
The component that other add as required, if expect that response speed can add low viscous liquid crystal material (fluorinated liquid crystal, hexamethylene lopps liquid crystal) faster, if expect that higher contrast gradient can add the liquid crystal material (as alkyne type liquid crystal) with large degree of birefringence, if want to realize colored demonstration, can add dichroic dye, if want that the cohesiveness that reduces working viscosity raising liquid crystal sylphon can add UV glue.
In novel smectic A phase liquid crystal material of the present invention, also can not contain the ester liquid crystal material shown in logical formula II, if not containing the ester liquid crystal material shown in (II), driving voltage can uprise.
Heterocyclic liquid crystal material used in the present invention and ester liquid crystal material can obtain by general chemosynthesis or other commercial sources, and other complementary materials are such as nematic phase formula, other liquid crystal monomers or organic ionic compounds can directly be purchased acquisition from the market.
Heterocycle liquid crystal and ester liquid crystal material preparation method in logical formula I and logical formula II are exemplified below:
Representative monomers is listed as follows table 1:
Table 1 leads to the synthetic illustrative list of monomer in formula I, (II)
Figure BDA00002118739100111
The preparation of L1:
The preparation of L1 intermediate 1:
In three mouthfuls of round bottom reaction flasks, added successively 23g (1.1eq) 1-bromine normal heptane, 37g (1.0eq.) triphenylphosphine, nitrogen purge post-heating stirs 5h.Suction strainer reaction solution, 200ml*3 ethyl acetate washing for filter cake.After dry, obtain 33g white solid 1.
The preparation of L1 intermediate 2:
Under anhydrous and oxygen-free condition, in four-hole round bottom reaction flask, add successively 100mL dry THF, 33g (1.2eq) intermediate 1, reaction system cools to-40 ℃ and drips 35ml n-Butyl Lithium, is warming up to 0 ℃ and stirs 1h after dripping off.Again reaction system is cooled to after-15 ℃, drips the bromo-5 aldehyde pyridines of 11.6g (1.2eq) 2-, dropwise rear temperature rising reflux and stir 3h.Reaction solution is after hydrolysis, and with petroleum ether extraction, then column chromatography obtains 11g intermediate 2.[H-NMR (400M, CDCl 3) δ (ppm): 8.6 (s, 1H), 7-8 (d, 2H), 6.5 (d, 1H), 6.1 (m, 1H), 1.2-1.4 (m, 8H), 0.95 (m, 3H)].
The preparation of L1 intermediate 3:
In four-hole round bottom reaction flask, add successively 50mL dehydrated alcohol, 10g (1.0eq) intermediate 2, reaction system deoxidation, then add palladium carbon (0.1g), then pass into H2,40 ℃ of stirring reaction 8h, reacting liquid filtering is removed palladium carbon, and concentration of reaction solution obtains common 10.0g intermediate 3.[H-NMR(400M,CDCl 3)δ(ppm)：8.6(s,1H),7-8(d,2H),2.6(m,2H),1.2-1.7(m,12H),0.95(m,3H)]。
The preparation of L1:
In reaction flask, add successively 40mL dehydrated alcohol, 40mL deionized water, 13g (2.5eq) salt of wormwood, 10g (1.0eq) intermediate 3,6.2g (1.2eq) 4-fluorobenzoic boric acid, reaction system deoxidation, then adds Pd (dppf) 2cl 2meter (0.1g), temperature rising reflux reaction 8h, 100mL ethyl acetate extraction for reaction solution, through column chromatography purification, obtains common 9.0g product.[H-NMR(400M,CDCl 3)δ(ppm)：8.6(s,1H),7-8(d,6H),2.6(m,2H),1.2-1.7(m,12H),0.95(m,3H)]。
The preparation of L2:
Adopt with the identical technique of L1, difference is to use different raw material 4-propylbenzene boric acid.L2[H-NMR(400M,CDCl3)δ(ppm)：8.6(s,1H),7-8(d,6H),2.6(m,4H),1.2-1.7(m,14H),0.95(m,6H)]。
The preparation of L4:
Adopt with the identical technique of L1, difference is to use different raw materials to cyanophenylboronic acid.L4[H-NMR(400M,CDCl3)δ(ppm)：8.6(s,1H),7-8(d,6H),2.6(m,2H),1.2-1.7(m,12H),0.95(m,3H)]。
The preparation of L3:
Adopt with L1 intermediate and prepare identical technique, preparation L3 intermediate 1, L3 intermediate 2, L3 intermediate 3.
The preparation of L3 intermediate 4:
In reaction flask, add successively 20mL dehydrated alcohol, 10mL deionized water, 13g (2.5eq) salt of wormwood, 5.1g (1.0eq) intermediate 3,3.4g (1.3eq) 4-amido phenylo boric acid, reaction system deoxidation, then adds Pd (Ph 3p) 4meter (0.05g), temperature rising reflux reaction 8h, reaction solution, through column chromatography purification, obtains common 5.2g product.[H-NMR(400M,CDCl3)δ(ppm)：8.6(s,1H),7-8(d,6H),5.4(s,2H),2.6(m,2H),1.2-1.7(m,12H),0.95(m,3H)]。
The preparation of L3:
In reaction flask, 5.0g (1.0eq.) L3 intermediate 4 is dissolved in to 30mL methylene dichloride, adds 15mL water, 5.3g (3eq.) calcium carbonate, reaction system is cooled to 0 ℃, drips 2.65g (1.3eq.) thiophosgene, and 0 ℃ is stirred 6h, reaction solution is through column chromatography, and purifying obtains 4.2g product.[H-NMR(400M,CDCl3)δ(ppm)：8.6(s,1H),7-8(d,6H),2.6(m,2H),1.2-1.7(m,12H),0.95(m,3H)]。
The preparation of L5:
The preparation of L5 intermediate 1:
In reaction system, add solvent DMF (being dried), the bromo-5-pyridone of 5g (1.0eq.) 2-, 6.1g (1.1eq.) 1-bromooctane, 9.9g (2.5eq.) salt of wormwood, 0.5g (0.1eq.) potassiumiodide, stir, 90 ℃ of reaction 4h, obtain 8.0g product 1 after reaction solution purifying.[H-NMR(400M,CDCl3)δ(ppm)：8.7(s,1H),7-8(d,2H),4.1(m,2H),1.2-1.7(m,12H),0.95(m,3H)]。
The preparation of L5 intermediate 2:
In reaction system, add successively 30mL dehydrated alcohol, 30mL deionized water, 7.0g (1.0eq) L5 intermediate 1,8.44g (2.5eq) salt of wormwood, 4.4g (1.3eq) 4-amido phenylo boric acid, reaction system deoxidation, then adds Pd (Ph 3p) 4meter (0.1g), temperature rising reflux reaction 16h, reaction solution, through column chromatography purification, obtains common 6.5g product 2.[H-NMR(400M,CDCl3)δ(ppm)：8.5(s,1H),7-8(d,6H),5.1(s,2H),4.0(m,2H),1.2-1.7(m,12H),0.95(m,3H)]。
The preparation of L5:
In reaction flask, 6.0g (1.0eq.) L5 intermediate 2 is dissolved in to 20mL methylene dichloride, adds 10mL water, 6.0g (3eq.) calcium carbonate, reaction system is cooled to 0 ℃, drips 3.0g (1.3eq.) thiophosgene, and 0 ℃ is stirred 6h, reaction solution is through column chromatography, and purifying obtains 5.5g product.[H-NMR(400M,CDCl3)δ(ppm)：8.5(s,1H),7-8(d,6H),3.9(m,2H),1.2-1.7(m,12H),0.95(m,3H)]。
The preparation of L6:
The preparation of L6 intermediate 1:
In reaction flask, add 82.8g (1.2eq.) salt of wormwood, 100ml morpholine, stirring, thermometer, constant pressure funnel are installed, and bottle is outer to be cooled to below 0 ℃, starts to drip 71g (1.0eq.) n-nonyl aldehyde, within approximately 30 minutes, dropwise, at 0～5 ℃, keep 8 hours, suction strainer reaction solution, filtrate is concentrated several times with 200ml sherwood oil (90-105 ℃), to rinse funnel, 94～96 ℃/product is collected in underpressure distillation, obtains 52g colourless liquid product 1.
The preparation of L6 intermediate 2:
In reaction flask, add 100ml methylene dichloride, 18g (1.2eq.) triethyl orthoformate and 21g (1.0eq.) L6 intermediate 1.Stirring, thermometer and dropping funnel are installed, be cooled to below-40 ℃, start to drip 17g (1.2eq.) boron trifluoride ether solution, dropping process temperature control is at-40～-45 ℃, within approximately 1 hour, dropwise,-40 ℃ of following maintenances 3 hours, naturally be warming up to 25 ℃, add 3g sulfuric acid 57ml water and the hydrolysis of 12ml alcohol mixeding liquid 3 hours, separatory, twice of dichloromethane extraction of water layer, merge organic phase, 5% wet chemical is washed three times, is washing with water to neutrality, use anhydrous magnesium sulfate drying organic phase, the concentrated 19g intermediate 2 that obtains.
The preparation of L6 intermediate 3:
In reaction system, add 150ml methyl alcohol; add 2.5g sodium silk; heat release back flow reaction makes sodium methoxide solution; be cooled to after 25 ℃; add 19.7g (1.0eq.) p-nitrophenyl amitraz hydrochloride; 28g (1.5eq.) L6 intermediate 2; logical N2 protection, 30 ℃ of temperature controls, react approximately 30 hours; reaction solution-10 are ℃ freezing; suction strainer, a small amount of sherwood oil for filter cake (cold) filter wash cake 3 times, then wash filter cake with water 3 times; blot 3 times of ethanol of rear use and heavily tie 1 time, obtain product 6g off-white color solid L6 intermediate 3.[H-NMR(400M,CDCl 3)δ(ppm)：8.3(s,2H),7-8(d,4H),2.7(m,2H),1.2-1.7(m,10H),0.95(m,3H)]。
The preparation of L6 intermediate 4:
In single port reaction flask, add 6g (1.0eq.) L6 intermediate 3, palladium carbon 2g, ethanol 200ml, after nitrogen purge, be warming up to 60 degrees Celsius and slowly drip 6g (2.0eq.) hydrazine hydrate, drip off backflow 1h, reaction solution is cooled to 25 ℃, suction strainer, filtrate is concentrated with 2 times of sherwood oil recrystallizations, obtains 4.5g off-white color solid L6 intermediate 4.[H-NMR(400M,CDCl 3)δ(ppm)：8.3(s,2H),7-8(d,4H),5.6(m,2H)，2.7(m,2H),1.2-1.7(m,10H),0.95(m,3H)]。
The preparation of L6:
In there-necked flask, add 4.5g (1.0eq.) L6 intermediate 4, chloroform 30ml, 5g (2.5eq.) calcium carbonate, deionized water 20ml, T=0 ℃, drips thiophosgene 5g (1.6eq.), drips off temperature control T=0-5 ℃ and stirs 3h.Suction strainer, filter cake 200ml washed with dichloromethane, filtrate separatory, after concentrating, column chromatography obtains 4g white solid product.[H-NMR(400M,CDCl 3)δ(ppm)：8.3(s,2H),7-8(d,4H),2.7(m,2H),1.2-1.7(m,10H),0.95(m,3H)]。
The preparation of L7:
L7 intermediate 1, first three processing method that the preparation of L7 intermediate 2 and L7 is prepared with L6 is identical, and difference is, has prepared after L7 intermediate 2, and direct reaction is prepared L7, and raw materials used is 3,4-difluorobenzene carbonamidine.
L7 finished product [H-NMR (400M, CDCl 3) δ (ppm): 8.5 (s, 2H), 7-8 (d, 3H), 2.7 (m, 2H), 1.2-1.7 (m, 10H), 0.95 (m, 3H)].
The preparation of L8 (a lot of synthetic methods of this type of monomer are all feasible, enumerate method comparatively easily herein):
In reaction system, add 120mL methylene dichloride, 15g (1.0eq.) 4-amylbenzene formic acid, 12.5g (1.02eq.) 3-fluoro-4-nitrophenol, 16.9g (1.05eq.) DCC, catalytic amount (0.05g) DMAP, stirs, 30 ℃ of reaction 8h.Aftertreatment, obtains 20g product.[H-NMR(400M，CDCl 3)δ：(ppm)7-8(d，7H)，2.5(m，2H),1.2-1.7(m，8H),0.95(m，3H)]。
The preparation of L9:
Preparation method is just the same with L8, and difference is only to have used 2-fluoro-4-amylbenzene formic acid and the fluoro-4-cyanophenol of 3-.[H-NMR(400M,CDCl 3)δ：(ppm)7-8(d，6H)，2.5(m，2H),1.2-1.7(m，8H),0.95(m，3H)]。
The preparation of L10:
Preparation method is just the same with L8 method, and difference is to have used the fluoro-4-pyridone of 2-.[H-NMR(400M,CDCl 3)δ：(ppm)8.4(s,1H)，7-8(d，6H)，2.5(m，2H),1.2-1.7(m，8H),0.95(m，3H)]。
The preparation of L11:
Preparation method is just the same with L8 method, and difference is to have used the fluoro-4-hydroxyl phenol of 2-and 5-octyloxy-2-pyridine carboxylic acid.[H-NMR(400M,CDCl 3)δ：(ppm)9.0(s,1H)，7-8.5(d，5H),4.0(m，2H),1.2-1.7(m，12H),0.95(m，3H)]。
Advantage of the present invention:
1, smectic A phase dispensing liquid crystal material of new generation of the present invention is applied in existing smectic liquid crystal display device, can effectively avoids the appearance of afterimage of image.
2, smectic A phase dispensing liquid crystal material of new generation of the present invention is applied in existing smectic liquid crystal display device, can effectively improves the contrast gradient of existing display device.Human eye acceptable contrast gradient is generally 5:1, and smectic A phase dispensing liquid crystal material of new generation provided by the invention can be greater than 10, good visual effect without any auxiliary lower its contrast gradient of photoprocess.
3, smectic A phase dispensing liquid crystal material driving voltage of new generation of the present invention lower (20～50V), more energy-conservation.
Below by the drawings and specific embodiments, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Accompanying drawing explanation
Fig. 1-a, Fig. 1-b and Fig. 1-c are respectively several different states of smectic A phase liquid crystal display, and Fig. 1-a is the state that shows image, and Fig. 1-b is the state that the image of demonstration cannot be wiped ghost, and Fig. 1-c is the state that image can be wiped completely.
Fig. 2 is that smectic liquid crystal drives displaying principle schematic diagram.
Fig. 3-a, Fig. 3-b and Fig. 3-c are the different operating principles of a few quasi-representative smectic A phases, wherein, Fig. 3-a be take the first-generation smectic A phase material that 8CB is representative, Fig. 3-b be take the s-generation smectic A phase material that siloxanes liquid crystal is representative, and Fig. 3-c be take the smectic A of a new generation's (third generation) phase material that heterocycle liquid crystal is representative.
Fig. 4 is 2.8 cun of liquid crystal sylphons.
Fig. 5 is 2.8 cun of screens filling sealing liquid crystal and bind IC.
Fig. 6 is the driving test macro of 2.8 cun of screens.
Fig. 7 is the instrumentation diagram of microscopy test comparison degree.
Fig. 8 is beneficial to dimming glass prepared by the present invention.
Embodiment
In the present invention, according to following mixed crystal experimentation, carry out mixed crystal and test:
1, first various liquid crystal materials are weighed to scale, join one by one in phial;
2, the phial that weighs up material is put into in baking oven, to be heated to liquid crystal completely limpid;
3, by ultrasonic concussion or magnetic agitation, liquid crystal is fully mixed evenly;
4, the liquid crystal mixing is filled in the liquid crystal sylphon of 12 micron thickness by crystal-pouring machine heating under vacuum, liquid crystal sylphon is of a size of 2.8 cun, as shown in Figure 4, in sylphon, contain the spacer of 12 microns, upper lower-glass is carved with ITO electrode towards the one side of spacer, every sheet glass is carved with 72 row 184 row ITO electrodes, and row is pixel with row intersection, and sylphon leaves place blow-by as irrigation crystal mouth with sealant sealing around.
5, the cooling rear use UV rubber seal mouth of liquid crystal cell, is then tied to the integral control circuit that drives chip with IC on the electrode of liquid crystal sylphon (as shown in Figure 5).
6, the IC chip of above-mentioned liquid crystal cell is connected to drive circuit board, by external source (0～70V voltage of alternating current can be provided) power supply, liquid crystal cell is driven, use 2KHz to carry out image scanning, thereby 30Hz wipes image to shielding frosted.Whole device as shown in Figure 6.
7, test the contrast gradient of above liquid crystal cell.
8, to above liquid crystal cell, the driving that circulates (is used high frequency map brushing picture as shown in Figure 1a incessantly, with low frequency frosted, wipe image as shown in Fig. 1 c) i.e. " aging " for some time, or room temperature carries out the scanning of image and frosted operation to it after standing for some time again, observe and whether have ghost.
To be device emptying light transmission rate under state and the ratio of the light transmission rate of device under frosted state to the contrast gradient of smectic liquid crystal indicating meter, generally all materials are basic identical at the light transmission rate emptying under state, so contrast gradient depends primarily on the light transmission rate of material under frosted state, the i.e. scattering states of smectic liquid crystal material.
Owing to there is no the standard detecting method to liquid crystal type display device contrast gradient to reflective smectic in industry, in experiment, adopt multiple commonplace and succinct contrast gradient testing method to test, finally selected a kind of testing method that more approaches human eye vision effect as checking and contrast standard.
Contrast gradient testing method: microscopy test
This testing method is relatively to commonly use and succinct testing method, its measuring result more approaches human eye, its device as shown in Figure 7, microscopy test comparison degree apparatus adopts light transmission rate measuring system HL-TT-MS, using the DM-2500M of Lai Ka company (Leica) type metaloscope is imaging device, using the MV-VD120SC of Wei Shi company (Microvision) type industrial CCD camera is light signal acquisition device, and using the HL-CR-11A of Han Lang company (Halation) software is numerical evaluation software.
Test process:
1, sample is positioned on Stage microscope, adjusts microscope (object lens) focal length and make sample blur-free imaging.
2, remove sample, each point value of using HL-CR-11A software to collect CCD is calculated as follows: Yi=0.299*R+0.587*G+0.114*B.
3, each point Yi value is sued for peace, obtain normalization coefficient Y0=Σ Yi.
4, sample is positioned on Stage microscope, uses now Y value of HL-CR-11A computed in software, Y=Σ Yi.
5, sample transmitance is defined as T=(Y/Y0) * 100%.
6,, for smectic liquid crystal sample, empty state transmitance Tc=(Yc/Y0) * 100%, frosted state transmitance Ts=(Ys/Y0) * 100%, contrast C r=Tc/Ts.
Briefly, first, Stage microscope is not placed liquid crystal cell, light source (light that the halogen lamp of microscope configuration sends) directly enters in the situation of object lens, use receptor to gather light, receptor converts the light ray energy collecting to corresponding electrical signal and is passed in the software in computer, and software records electrical signal B is now as basic reference point.Then, fixing light-source brightness L now, the height that liquid crystal cell is positioned over to Stage microscope and adjusts Stage microscope makes can clearly observe liquid crystal cell in eyepiece, receptor by the liquid crystal cell now collecting in empty with frosted state under light ray energy convert respectively electrical signal to and import computer into, computer software can contrast respectively empty with frosted state under the light ray energy that receives compare with the energy of light source of basic reference.That is: empty the light ray energy electrical signal Q receiving under state and divided by basic reference point B, obtain emptying the value QL of percent of pass under state, the light ray energy electrical signal M receiving under frosted state obtains the value ML of percent of pass under frosted state divided by basic reference point B, by the transmitance that empties state, divided by frosted state transmitance QL/ML*100%, obtain the value of contrast gradient.
The following examples are all mixed according to the mixed crystal method described in the present invention, and carry out contrast gradient test.
Embodiment mono-: use nematic phase formula respectively with the contrast that is mixed of siloxanes liquid crystal material, heterocyclic liquid crystal material
Table 2 nematic phase formula is mixed with siloxanes liquid crystal material, heterocyclic liquid crystal material respectively
Figure BDA00002118739100161
Figure BDA00002118739100171
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen, and sealing binding, tests its contrast gradient as above.PDLC-004 in embodiment mono-purchases in Shijiazhuang Hua Rui Science and Technology Ltd., and SLC1717 and 1L1117600-200 purchase in Shijiazhuang Yongshenghuaqing Liquid Crystal Co., Ltd.
Embodiment bis-: formula and performance thereof that the smectic A phase liquid crystal that the nitrogen heterocyclic ring of take is main body adds arbitrary ester liquid crystal.
The compositing formula of table 3 embodiment bis-mixed crystal
Figure BDA00002118739100172
Figure BDA00002118739100181
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment tri-: take formula and the performance thereof of adding arbitrary ester liquid crystal containing the pyridine heterocycle smectic A phase liquid crystal that is main body.
The compositing formula of table 4 embodiment tri-mixed crystal
Figure BDA00002118739100182
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment tetra-: take formula and the performance thereof of adding arbitrary ester liquid crystal containing the pyrimidine heterocyclic smectic A phase liquid crystal that is main body.
The compositing formula of table 5 embodiment tetra-mixed crystal
Figure BDA00002118739100191
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment five: formula and performance thereof that the smectic A phase liquid crystal that the oxygen heterocyclic ring of take is main body adds arbitrary ester liquid crystal.
The compositing formula of table 6 embodiment five mixed crystal
Figure BDA00002118739100192
Figure BDA00002118739100201
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment six: formula and performance thereof that the smectic A phase liquid crystal that the sulfur heterocyclic ring of take is main body adds arbitrary ester liquid crystal.
The compositing formula of table 7 embodiment six mixed crystal
Figure BDA00002118739100202
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment seven: the smectic A phase liquid crystal that the boracic heterocycle of take is main body adds formula and the performance thereof of arbitrary or more than one ester liquid crystals.
The compositing formula of table 8 embodiment seven mixed crystal
Figure BDA00002118739100203
Figure BDA00002118739100211
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment eight: the smectic A phase liquid that the various mixing heterocycle arbitrary combination of take are main body adds crystal formulations and the performance thereof of arbitrary or more than one ester liquid crystals.
The compositing formula of table 9 embodiment eight mixed crystal
Figure BDA00002118739100212
Figure BDA00002118739100221
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment nine: the smectic A phase liquid crystal that the various mixing heterocycle arbitrary combination of take are main body adds formula and the performance thereof of arbitrary or more than one ester liquid crystals.
The compositing formula of table 10 embodiment nine mixed crystal
Figure BDA00002118739100222
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment ten: take heterocycle as main body, add arbitrary or more than one ester liquid crystals formula in, introduce smectic A phase dispensing liquid crystal and performance thereof that alkyne type liquid crystal material improves contrast gradient.
The compositing formula of table 11 embodiment ten mixed crystal
Figure BDA00002118739100231
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 18:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment 11: as main body, add in the formula of arbitrary ester liquid crystal take heterocycle, introduce smectic A phase dispensing liquid crystal and performance thereof that low viscosity liquid crystal material reduces driving voltage.
The compositing formula of table 12 embodiment 11 mixed crystal
Figure BDA00002118739100232
Figure BDA00002118739100241
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 20 ~ 30V.
Embodiment 12: as main body, add in the formula of arbitrary ester liquid crystal take heterocycle, introduce two tropism's dyestuffs and reach colored smectic A phase dispensing liquid crystal and the performance thereof showing.
The compositing formula of table 13 embodiment 12 mixed crystal
Figure BDA00002118739100242
Figure BDA00002118739100251
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen, and sealing binding, obtains red-purple display screen.Testing its contrast gradient is 12:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment 13: as main body, add in the formula of arbitrary ester liquid crystal take heterocycle, add UV glue to reduce close-burning smectic A phase dispensing liquid crystal and performance thereof that construction temperature improves liquid crystal cell.
The compositing formula of table 14 embodiment 13 mixed crystal
Figure BDA00002118739100252
Under above mixed crystal room temperature, be limpid state, by above mixed crystal room temperature priming by vacuum to 2.8 cun screen, sealing binding, UV solidifies to such an extent that smectic A phase liquid crystal shows screen.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 30 ~ 40V.
Embodiment 14: with any heterocycle, be combined as smectic A phase dispensing liquid crystal and the performance thereof that main body is not added ester liquid crystal.
The compositing formula of table 15 embodiment 14 mixed crystal
Figure BDA00002118739100261
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 40 ~ 50V.
Embodiment 15: formula and performance thereof that the smectic A phase liquid crystal that the nitrogen heterocyclic ring of take is main body does not add arbitrary ester liquid crystal.
The compositing formula of table 16 embodiment 15 mixed crystal
Figure BDA00002118739100262
Figure BDA00002118739100271
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 40 ~ 50V.
Embodiment 16: take formula and the performance thereof of not adding arbitrary ester liquid crystal containing the pyridine heterocycle smectic A phase liquid crystal that is main body.
The compositing formula of table 17 embodiment 16 mixed crystal
Figure BDA00002118739100272
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 40 ~ 50V.
Embodiment 17: take formula and the performance thereof of not adding arbitrary ester liquid crystal containing the pyrimidine heterocyclic smectic A phase liquid crystal that is main body.
The compositing formula of table 18 embodiment 17 mixed crystal
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 40 ~ 50V.
Embodiment 18: formula and performance thereof that the smectic A phase liquid crystal that the oxygen heterocyclic ring of take is main body does not add arbitrary ester liquid crystal.
The compositing formula of table 19 embodiment 18 mixed crystal
Figure BDA00002118739100282
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 40 ~ 50V.
Embodiment 19: formula and performance thereof that the smectic A phase liquid crystal that the sulfur heterocyclic ring of take is main body does not add arbitrary ester liquid crystal.
The compositing formula of table 20 embodiment 19 mixed crystal
Figure BDA00002118739100291
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 40 ~ 50V.
Embodiment 20: formula and performance thereof that the smectic A phase liquid crystal that the boracic heterocycle of take is main body does not add arbitrary ester liquid crystal.
The compositing formula of table 21 embodiment 20 mixed crystal
Figure BDA00002118739100292
Figure BDA00002118739100301
Above mixed crystal is heated in limpid priming by vacuum to 2.8 cun screen to sealing binding.Testing its contrast gradient is 11:1, aging 5000 times without ghost, driving voltage 40 ~ 50V.
Smectic A phase dispensing liquid crystal of the present invention can also be used as dimming medium, increases pixel increase glass size and can obtain large-sized dimming glass (as shown in Figure 8).
Smectic A phase liquid crystal material formula of new generation of the present invention is not only different from the first-generation, s-generation smectic A phase liquid crystal before principle of work, and the smectic A before being also obviously better than on practical application effect fills a prescription mutually.Smectic A of the present invention fills a prescription mutually and is applied to after display device, and the long-term placement of image of demonstration can be wiped completely and do not stayed ghost, and long-term driving used rear its image also can wipe completely, and its contrast gradient height is generally greater than 10, and driving voltage is low generally at 20 ~ 50V.

Claims (10)

1. a novel smectic A phase liquid crystal material, is characterized in that: comprise the heterogeneous ring compound that at least one represents with general formula (I):
Figure FDA00002118739000011
Logical formula I
The positive integer that wherein n is 1 ~ 4, m and p are 0 or 1 ~ 4 positive integer, M1 and M3 are 0 or 1 ~ 2 positive integer, the positive integer that M2 is 1 ~ 2;
X, Z are phenyl ring, and F is fluorine atom, and on phenyl ring, any hydrogen atom can be replaced by fluorine atom; When Y is phenyl ring, T is nitrogen-atoms, and the either carbon atom on phenyl ring all can be replaced by nitrogen-atoms; When Y is hexamethylene ring, T is oxygen, sulphur and/or boron atom, and the either carbon atom on hexamethylene ring can be replaced by oxygen, sulphur and/or boron atom;
A, B are selected from a kind of in following groups: CN, F, NCS, NCO, CF 3, CHF 2, CH 2f, OCF 3, OCHF 2, OCH 2f, NO 2, Cl, CH=CF 2and OCH=CF 2; The alkene oxygen base of the thiazolinyl of the alkyl of C1-C20, the alkoxyl group of C1-C20, C1-C20, C1-C20, the silylation of C1-C20, the siloxanes of C1-C20 and halides corresponding to above-mentioned group; Arbitrary-CH 2-quilt-O-,-S-,-CF 2-,-CF 2o-,-CO-,-COO-,-O-CO-,-O-COO-,-CF=CF-,-CH=CF-,-CF=CH-or-alkyl of C1-C20 that CH=CH-replaces is, alkene oxygen base and the isomer thereof of the thiazolinyl of the alkoxyl group of C1-C20, C1-C20 and C1-C20.
2. novel smectic A phase liquid crystal material according to claim 1, is characterized in that: also comprise the ester compound that at least one represents with general formula (II):
Figure FDA00002118739000012
Logical formula II
Wherein n1, n2 are 0 or 1 ~ 4 positive integer, and n3 is 0 or 1 ~ 2 positive integer, and n4 is 0 or 1 ~ 3 positive integer;
C and D are phenyl ring, S 1and S 2for N atom or F atom, work as S 1and S 2for the arbitrary C atom of N atomic time on can substituted benzene ring, work as S 1and S 2for the arbitrary H atom of F atomic time on can substituted benzene ring;
R 1, R 2be selected from a kind of in following groups: CN, F, NCS, NCO, CF 3, CHF 2, CH 2f, OCF 3, OCHF 2, OCH 2f, NO 2, Cl, CH=CF 2and OCH=CF 2; Alkene oxygen base, the silylation of C1-C20 and the siloxanes of C1-C20 of the thiazolinyl of the alkyl of C1-C20, the alkoxyl group of C1-C20, C1-C20, C1-C20 and halides corresponding to above-mentioned group; Arbitrary-CH 2-quilt-O-,-S-,-CF 2-,-CF 2o-,-CO-,-COO-,-O-CO-,-O-COO-,-CF=CF-,-CH=CF-,-CF=CH-or-alkyl of C1-C20 that CH=CH-replaces is, alkene oxygen base and the isomer thereof of the thiazolinyl of the alkoxyl group of C1-C20, C1-C20 and C1-C20.
3. novel smectic A phase liquid crystal material according to claim 2, is characterized in that: also comprise at least one ionic compound.
4. novel smectic A phase liquid crystal material according to claim 3, is characterized in that: also comprise nematic liquid crystal monomer or, to row liquid crystal monomer or bar-shaped compound.
5. novel smectic A phase liquid crystal material according to claim 4, is characterized in that: also comprise dichroic dye or UV glue.
6. novel smectic A phase liquid crystal material according to claim 1, is characterized in that: described at least one of take in the compound that heterogeneous ring compound that general formula (I) represents represents as general formula (III) to general formula (VII),
Figure FDA00002118739000021
Logical formula III
Figure FDA00002118739000022
Logical formula IV
Figure FDA00002118739000023
General formula (V)
Figure FDA00002118739000031
Logical formula VI
Figure FDA00002118739000032
General formula (VII)
In general formula (III) to (VII), letter character representative implication is with logical formula I.
7. novel smectic A phase liquid crystal material according to claim 2, is characterized in that: described take ester compound that general formula (II) represents as general formula (VIII), (XIII) and (XIV) at least one in the compound of expression,
Figure FDA00002118739000033
General formula (VIII)
Figure FDA00002118739000034
General formula (X III)
Figure FDA00002118739000035
General formula (X IV)
N6 is 0 or 1 ~ 2 positive integer; Other alphabetical implications in above-mentioned general formula are with logical formula II.
8. novel smectic A phase liquid crystal material according to claim 3, is characterized in that: described ionic compound is selected from sodium lauryl sulphate, ethyltriphenylphosphiodide iodide phosphine, (ferrocenyl methyl) trimethylammonium ammonium iodide, 1,2-dimethyl-3-butyl imidazole hexafluorophosphate, tetraethyl-amine p-toluenesulfonic esters, phenyl triethyl iodate ammonium, 1-octyl group-3-Methylimidazole hexafluorophosphate, two (tetra-n-butyl amines) two (1,3-dithiole-2-thioketones-4,5-bis-mercaptan) palladium, tetra-n-butyl closes two (1,3-dithiole-2-thioketones-4,5-bis-mercaptan) nickel, two (tetra-n-butyl ammoniums) close two (1,3-dithiole-2-thioketones-4,5-bis-mercaptan) zinc, two (tetra-n-butyl ammoniums) close four cyano biphenol quinone bismethane, Tetrabutyl amonium bromide, hexadecyl ammoniumper chlorate, hexadecyl bromination four ammoniums, 1-butyl-3-Methylimidazole tetrachloro ferrate, methyl triphenyl phosphonium iodide, tetraphenylphosphoniiodide iodide phosphine, cetyl trimethylammonium bromide, cetyl trimethyl ammoniumper chlorate, cetalkonium chloride, dodecylpyridinium bromide, bromohexadecane yl pyridines, chloro-hexadecane yl pyridines, with one or more in hexadecyl tributyl phosphonium ammonium.
9. the application of the novel smectic A phase liquid crystal material described in any one in smectic liquid crystal display device or light modulation device in claim 1-8.
In claim 1-8 the novel smectic A phase liquid crystal material described in any one in the liquid crystal display device of the double frequency drive pattern that uses low frequency frosted and high frequency to empty or the application in light modulation device.
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